CN108473807B

CN108473807B - Liquid composition for ink-jet printer

Info

Publication number: CN108473807B
Application number: CN201680073852.0A
Authority: CN
Inventors: 梅林励
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2015-12-18
Filing date: 2016-11-10
Publication date: 2021-05-25
Anticipated expiration: 2036-11-10
Also published as: JP6556258B2; EP3392318A1; EP3392318A4; EP3392318B1; JPWO2017104318A1; CN108473807A; WO2017104318A1; US20180291218A1

Abstract

The present invention provides a liquid composition for an inkjet printer, which contains an organic solvent, a polymerizable compound having a weight average molecular weight of 1000 to 30000 inclusive, a (meth) acrylic-modified polyorganosiloxane which is a copolymer of a reactive polysiloxane having at least one of a polymerizable group and a mercapto group and having no polymerizable group and a weight average molecular weight of 20000 to 400000 inclusive, and a photopolymerization initiator, wherein the content of the organic solvent is 40 to 80 mass% inclusive relative to the total amount of the liquid composition, and the content of the (meth) acrylic-modified polyorganosiloxane is 0.1 to 5.0 mass% inclusive relative to the total amount of the liquid composition.

Description

Liquid composition for ink-jet printer

Technical Field

The present invention relates to a liquid composition for an ink jet printer.

Background

The ink jet technology is a technology for forming an image by ejecting a liquid composition (for example, ink) for an ink jet printer from an ink jet head of the ink jet printer (ink jet recording apparatus).

Various techniques are known as to the inkjet technique.

For example, as an inkjet recording method in which bleeding resistance and anti-blooming of a recorded image are good, a glossy feeling equivalent to that of offset printing can be obtained, and further, a projection, ejection stability and productivity, which are problems unique to a line-type inkjet head, are solved, among inkjet recording methods in which an inkjet ink is ejected from an inkjet recording head and recorded on a recording medium, there are known the following inkjet recording methods: the inkjet ink contains at least a coloring material and a polymer compound, the polymer compound has a plurality of side chains with respect to a hydrophilic main chain and is capable of crosslinking bonding between the side chains by irradiation with active energy rays, and the inkjet recording head is of a line-type inkjet head system, and recording is performed by controlling the relative humidity in the vicinity of the inkjet recording head to 40% RH or more and 95% RH or less (see, for example, japanese patent laid-open No. 2007 and 191701).

In addition, as a method for producing a building panel having sufficient weather resistance that can be durable outdoors, among methods for producing a building panel having an image formed by inkjet printing, a method for producing a building panel including the following steps is known: (1) performing ink jet coating with UV ink on the base material subjected to the undercoating coating; (2) curing the UV ink with ultraviolet rays after the step (1); (3) a step of applying a transparent coating to the surface subjected to the ink-jet coating after the step (2); the UV ink contains a photopolymerization initiator, a reactive oligomer and/or a reactive monomer, and a pigment, and the curing rate of the UV ink after curing in the step (2) is 50 to 90%, and the transparent coating contains a crosslinking component (see, for example, jp 2010-167334 a).

As an active energy ray-curable composition, an active energy ray-curable ink composition, and an inkjet recording method and printed matter using the active energy ray-curable ink composition, which are cured with high sensitivity even when irradiated with active energy rays of low power output, and which are less likely to bleed out a surfactant and excellent in aging stability, there are known an active energy ray-curable composition, an inkjet recording method using the active energy ray-curable ink composition, and a printed matter using the active energy ray-curable composition, the active energy ray-curable composition containing: (A) a polymerizable compound having an ethylenically unsaturated bond and being substantially insoluble in water; (B) a surfactant having 1 or more groups selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, and a methacrylamide group; (C) a polymerization initiator; and (D) water (see, for example, japanese patent laid-open publication No. 2011-208088).

As an image forming technique using an ink jet recording ink that can be cured or thickened by reaction upon irradiation with radiation such as visible light, ultraviolet light, electron beam, infrared ray, or the like, there is known an ink jet recording apparatus having the following mechanism: a radiation-curable ink containing a radiation-curable compound is ejected from an ink jet head to form an image on a recording medium which does not substantially absorb the ink, and the surface shape is adjusted after the ejected ink is cured or thickened by irradiation with radiation (see, for example, japanese patent laid-open No. 2003-276178).

As an inkjet ink having excellent image uniformity (reduction in the difference in gloss between an image portion and a non-image portion), sharpness (edge sharpness), bleed resistance, and improved adhesion resistance, there is known an inkjet ink containing at least a colorant, water, and a polymer compound having a plurality of side chains in a hydrophilic main chain and being capable of crosslinking bonding between the side chains by irradiation with active energy rays, and having a surface tension of 19mN/m or more and less than 35mN/m (see, for example, japanese patent application laid-open No. 2007-45936).

As an inkjet recording apparatus which can avoid poor ink curing due to different absorption characteristics of activation energy caused by different inks and can achieve an ideal curing process, there has been proposed an inkjet recording apparatus including an image forming unit including a nozzle row in which a plurality of nozzles for ejecting ink cured by irradiation with an activation light are arranged, an ejection control unit including a plurality of nozzle rows corresponding to a plurality of inks having different curing performances, and an activation light irradiation unit including a plurality of irradiation units for irradiating an activation light with the activation light; the discharge control means controls ink discharge for each of the divided units in which the nozzle row is divided into a plurality of units, so that the ink discharged from each of the divided units forms a layer on the recording medium, and controls ink discharge from the image forming means so that a plurality of layers formed by the inks discharged from the different divided units are stacked; the active light irradiation mechanism irradiates an active light to the ink ejected to the recording medium (see, for example, japanese patent laid-open No. 2012-101492).

In addition, as an ink that can print a high-definition image having no unevenness, high flatness, and a glossy feeling in an ink jet printer, there is known an ink that is obtained by adding n-hexane as a volatile organic solvent to a UV-curable ink that is composed of at least a pigment, an ultraviolet-curable resin cured by ultraviolet light, and a photopolymerization initiator and has a viscosity of 20mPa · sec or more (room temperature 25 ℃) and a viscosity of 3mPa · sec or more and 18mPa · sec or less (room temperature 25 ℃) (see, for example, japanese patent application laid-open No. 2010-280828).

As a system for providing scratch resistance and reducing the scratch transition, a system for printing a durable inkjet ink image having sufficient rub resistance is known, which comprises a) a base material, b) a 1 st inkjet pen containing an inkjet ink composed of i) a 1 st liquid vehicle and ii) an effective amount of a pigment colorant, and c) a smoothing component, wherein the 1 st inkjet pen is configured to be ejected onto the base material; the smoothing component is configured to cover the inkjet ink once ejected onto the substrate (see, for example, japanese patent laid-open No. 2004-284362).

Disclosure of Invention

Technical problem to be solved by the invention

However, in the ink jet technology, there is a case where it is required to improve the abrasion resistance of the formed image. As a case where improvement in abrasion resistance of an image is required, for example, decorative printing is performed on a soft base material such as leather by an ink jet technique.

However, images formed by the ink jet techniques described in japanese patent laid-open nos. 2007 and 191701, 2010 and 167334, 2011 and 208088, 2003 and 276178, 2007 and 45936, 2012 and 101492, 2010 and 280828, and 2004 and 284362 may have insufficient abrasion resistance.

According to the studies of the present inventors, it has been found that when a polymerizable compound having a weight average molecular weight of 1000 or more and 30000 or less and a specific (meth) acrylic acid-modified polyorganosiloxane are contained in a liquid composition for an ink jet printer, the abrasion resistance of an image formed is improved.

However, according to the studies of the present inventors, it has been found that when these components are contained in the liquid composition for an inkjet printer, the ejection stability of the ink ejected from the inkjet head may be impaired.

One embodiment of the present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid composition for an inkjet printer which is excellent in ejection stability from an inkjet head and can form an image excellent in abrasion resistance.

Means for solving the technical problem

The means for solving the above problem include the following means.

< 1 > a liquid composition for inkjet printers, comprising an organic solvent, a polymerizable compound having a weight average molecular weight of 1000 or more and 30000 or less, a (meth) acrylic acid-modified polyorganosiloxane which is a copolymer of a reactive polysiloxane having at least one of a polymerizable group and a mercapto group and a (meth) acrylate and which has no polymerizable group and has a weight average molecular weight of 20000 or more and 400000 or less, and a photopolymerization initiator,

the content of the organic solvent is 40 to 80 mass% based on the total amount of the liquid composition,

the content of the (meth) acrylic acid-modified polyorganosiloxane is 0.1 mass% or more and 5.0 mass% or less with respect to the total amount of the liquid composition.

< 2 > the liquid composition for inkjet printers as described in < 1 >, wherein the polymerizable compound is a 2-functional acrylate compound.

The liquid composition for an ink jet printer as described in < 3 > such as < 1 > or < 2 >, wherein the content of the polymerizable compound is 5% by mass or more and 40% by mass or less with respect to the total amount of the liquid composition.

The liquid composition for an ink jet printer described in any one of < 4 > to < 1 > -3 > containing particles composed of the (meth) acrylic acid-modified polyorganosiloxane, wherein the volume average primary particle diameter of the particles is 0.01 μm or more and 0.3 μm or less.

< 5 > the liquid composition for inkjet printers as defined in any one of < 1 > -4 >, wherein the reactive polysiloxane is at least one compound represented by the following formula (I).

[ chemical formula 1]

In the formula (I), R¹、R²And R³Independently represents a C1-20 alkyl group, a C1-20 halogenated alkyl group, or a C1-20 alkoxy group, Y represents an organic group having at least one of a polymerizable group and a mercapto group, Z¹And Z²Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by the formula (Z), m represents an integer of 1 to 10000, and n represents an integer of 1 or more.

In the formula (Z), R⁴And R⁵Each independently represents a C1-20 alkyl group, a C1-20 halogenated alkyl group, or a C1-20 alkoxy group, R⁶Represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, or an organic group having at least one of a polymerizable group and a mercapto group, and represents a bonding position.

< 6 > such as < 5 >, wherein Y in formula (I) is a mercaptoalkyl group having 1 to 20 carbon atoms,

r in the formula (Z)⁶Is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, or a mercaptoalkyl group having 1 to 20 carbon atoms.

[ 7 ] the liquid composition for an ink jet printer according to any one of the claims < 1 > to < 6 >, wherein the (meth) acrylate is at least one compound represented by the following formula (II).

[ chemical formula 2]

In the formula (II), R⁷Represents a hydrogen atom or a methyl group, R⁸Represents an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms,A hydroxyalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

Effects of the invention

According to one embodiment of the present invention, there is provided a liquid composition for an inkjet printer, which is excellent in ejection stability from an inkjet head and can form an image excellent in abrasion resistance.

Detailed Description

The present invention will be described in detail with reference to specific embodiments, but the present invention is not limited to the embodiments.

In the present specification, the numerical range indicated by "to" includes ranges in which the numerical values recited before and after "to" are respectively the minimum value and the maximum value.

In the present specification, the amount of each component in the composition refers to the total amount of a plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition.

In the present specification, the term "step" means not only an independent step, but also includes a step that can achieve the intended purpose of the step even when the step is not clearly distinguished from other steps.

In the present specification, "light" is a concept including active energy rays such as γ rays, β rays, electron beams, ultraviolet rays, visible rays, infrared rays, and the like.

In the present specification, ultraviolet rays are sometimes referred to as "uv (ultra violet)".

In the present specification, "(meth) acrylic acid" is a concept including both acrylic acid and methacrylic acid, "(meth) acrylate" is a concept including both acrylate and methacrylate, and "(meth) acryloyl group" is a concept including both acryloyl group and methacryloyl group.

Liquid composition for ink-jet printer

The disclosed liquid composition for an inkjet printer (hereinafter, also simply referred to as "liquid composition") contains an organic solvent, a polymerizable compound having a weight average molecular weight of 1000 or more and 30000 or less, a (meth) acrylic-modified polyorganosiloxane which is a copolymer of a reactive polysiloxane having at least one of a polymerizable group and a mercapto group and having no polymerizable group and a weight average molecular weight of 20000 or more and 400000 or less (hereinafter, also referred to as "specific (meth) acrylic-modified polyorganosiloxane"), and a photopolymerization initiator, wherein the content of the organic solvent is 40% by mass or more and 80% by mass or less relative to the total amount of the liquid composition, and the content of the specific (meth) acrylic-modified polyorganosiloxane is 0.1% by mass or more and 5.0% by mass or less relative to the total amount of the liquid composition.

The liquid composition of the present disclosure has excellent ejection stability from an inkjet head (hereinafter, also referred to as "IJ ejection stability") and can form an image having excellent abrasion resistance.

The reason why the liquid composition of the present disclosure can exert the effect of improving the abrasion resistance of an image is presumed as follows.

It is presumed that one of the reasons for improving the abrasion resistance of an image is that the formed image is cured by light. In detail, since the liquid composition of the present disclosure contains the polymerizable compound and the photopolymerization initiator, when an image is formed using the liquid composition of the present disclosure, the formed image can be cured by light.

Another reason why the abrasion resistance of an image is improved is presumed to be that smoothness is imparted to the image by the polyorganosiloxane skeleton in the specific (meth) acrylic acid-modified polyorganosiloxane.

Another reason for improving the abrasion resistance of an image is presumed as follows. That is, since the specific (meth) acrylic acid-modified polyorganosiloxane is a copolymer of a reactive polysiloxane and a (meth) acrylate, a polymer chain of the (meth) acrylate (hereinafter, also referred to as a "(meth) acrylic acid chain") is present in the molecule. It is considered that in an image formed from the liquid composition of the present disclosure, the polyorganosiloxane skeleton of the specific (meth) acrylic acid-modified polyorganosiloxane is likely to be present not only on the surface of the image but also in the interior of the image due to the action of the (meth) acrylic acid chain. Therefore, even when the surface of the image is abraded to expose a new surface, the new surface has a polyorganosiloxane skeleton. Therefore, even when the image is repeatedly subjected to slight abrasion, the effect of improving the abrasion resistance by the polyorganosiloxane skeleton is continued, and thus it is considered that the excellent abrasion resistance of the image can be maintained.

The reason why the liquid composition of the present disclosure is excellent in IJ ejection stability can be presumed as follows.

It is considered that, in general, when a (meth) acrylic acid-modified polyorganosiloxane having a weight average molecular weight (hereinafter, also referred to as "Mw") of 20000 or more and a polymerizable compound having Mw of 1000 or more are contained in a liquid composition, the viscosity of the liquid composition tends to increase.

However, in the liquid composition of the present disclosure, it is considered that an increase in the viscosity of the liquid composition can be suppressed by setting the content of the organic solvent to 40 mass% or more, the content of the specific (meth) acrylic-modified polyorganosiloxane to 5.0 mass% or less, the Mw of the specific (meth) acrylic-modified polyorganosiloxane to 400000 or less, and the Mw of the polymerizable compound to 30000 or less. Therefore, excellent IJ ejection stability of the liquid composition can be maintained.

From the above reasons, it is considered that the liquid composition of the present disclosure is excellent in ejection stability from an inkjet head (hereinafter, also referred to as "IJ ejection stability") and can form an image excellent in abrasion resistance.

In the present specification, the weight average molecular weight refers to a value measured by Gel Permeation Chromatography (GPC).

The GPC was carried out using HLC-8020GPC (TOSOH CORPORATION), 3 TSKgel (registered trademark) and Super Multipore HZ-H (TOSOH CORPORATION, 4.6 mmID. times.15 cm) as a column, and THF (tetrahydrofuran) as an eluent.

GPC was performed using a differential Refractive Index (RI) detector with a sample concentration of 0.45 mass%, a flow rate of 0.35ml/min, a sample injection amount of 10. mu.l, and a measurement temperature of 40 ℃.

Calibration curves were prepared from "standard TSK standard, polystyrene" by TOSOH CORPORATION: 8 samples of "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", "A-1000" and "n-propylbenzene" were prepared.

Images formed from the liquid compositions of the present disclosure are also excellent in flexibility.

Here, the flexibility of an image means the ability of an image to easily follow the bending of a recording medium (for example, a base material) on which an image is formed when the recording medium is bent. If the flexibility of the image is poor, when the recording medium (for example, the base material) on which the image is formed is bent, the image cannot follow the bend of the recording medium, and cracks in the image are likely to occur. Such image cracks are particularly prone to occur in photocured images.

The reason why the image formed from the liquid composition of the present disclosure is excellent in the flexibility is considered to be that the Mw of the polymerizable compound is 1000 or more. That is, when an image formed from a liquid composition containing a polymerizable compound is cured by light, polymerization and crosslinking of the polymerizable compound proceed in the image in the process of photocuring the image. It is considered that when a polymerizable compound having Mw of 1000 or more is used as the polymerizable compound, the distance between the crosslinking points becomes long, and thus the image is easily bent. That is, even when the substrate on which the image is formed is curved, the image is likely to follow the curvature of the substrate, and cracks in the image are unlikely to occur. Thus, it is considered that the image formed from the liquid composition of the present disclosure is excellent in the flexibility.

The liquid composition of the present disclosure is particularly suitable for ink jet recording (for example, decorative printing) on a flexible substrate (leather or the like) as a recording medium because it can form an image having excellent abrasion resistance and bendability.

The polymerizable compound is preferably a 2-functional acrylate compound from the viewpoint of further improving the flexibility of an image.

Among them, 2-functional urethane acrylate compounds are particularly preferable.

The content of the polymerizable compound is preferably 5% by mass or more and 40% by mass or less with respect to the total amount of the liquid composition.

When the content of the polymerizable compound is 5% by mass or more, the abrasion resistance of the image is further improved. The content of the polymerizable compound is more preferably 10% by mass or more from the viewpoint of further improving the abrasion resistance of the image.

When the content of the polymerizable compound is 40% by mass or less, the IJ ejection stability of the liquid composition is further improved. From the viewpoint of further improving the IJ ejection stability of the liquid composition, the content of the polymerizable compound is more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

When the liquid composition contains a 2-functional acrylate compound as the polymerizable compound, the preferable range of the content of the 2-functional acrylate compound is also the same as the preferable range of the content of the polymerizable compound.

From the viewpoint of further improving the abrasion resistance of an image, the liquid composition preferably contains particles composed of a specific (meth) acrylic acid-modified polyorganosiloxane. In other words, the specific (meth) acrylic-modified polyorganosiloxane contained in the liquid composition is preferably in the form of particles.

The volume average primary particle diameter (hereinafter, also referred to as "particle diameter") of the particles is preferably 0.01 μm or more and 0.3 μm or less.

When the particle diameter of the particles is 0.01 μm or more, the abrasion resistance of the image is further improved. The particle diameter of the particles is preferably 0.05 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.15 μm or more.

When the particle diameter of the particles is 0.3 μm or less, the IJ ejection stability of the liquid composition is further improved. The particle diameter of the particles is more preferably 0.25 μm or less.

In the present specification, the volume average primary particle diameter (particle diameter) is a value measured using a laser diffraction/scattering particle size distribution measuring apparatus using tripropylene glycol methyl ether as a measuring solvent.

The liquid composition may further contain a colorant.

The manner in which the liquid composition contains the colorant is suitable in the case where the liquid composition is used as a coloring ink.

In this case, the content of the colorant is preferably 0.1% by mass or more.

Depending on the mode (coloring ink) in which the liquid composition contains the colorant, a colored image having excellent abrasion resistance can be formed.

The liquid composition is also preferably used as a colorless ink containing substantially no colorant.

In the present specification, the term "substantially free of a coloring agent" means that the content of the coloring agent is less than 0.1% by mass relative to the total amount of the liquid composition.

In the present specification, "colorless" means substantially colorless.

A colorless image having excellent abrasion resistance can be formed by a mode (colorless ink) in which the liquid composition does not substantially contain a colorant.

As an example of the colorless ink, a surface coating liquid for forming a colorless coating film (hereinafter, also referred to as a "surface coating film") on a colored image formed with the colored ink can be given. According to the top coating liquid as the liquid composition of the present disclosure, a top coating film excellent in abrasion resistance can be formed. By covering the colored image with such a top-coated film having excellent abrasion resistance, the abrasion resistance of the colored image (specifically, the colored image with the top-coated film) can be improved. In this case, the colored image covered with the top-coat film may be formed using a known coloring ink or a liquid composition of the present disclosure containing a colorant.

Next, preferred embodiments of the liquid composition of the present disclosure will be further described.

< specific (meth) acrylic acid-modified polyorganosiloxane >

The liquid composition of the present disclosure contains, as the specific (meth) acrylic-modified polyorganosiloxane, at least one (meth) acrylic-modified polyorganosiloxane which is a copolymer of at least one of reactive polysiloxanes having at least one of a polymerizable group and a mercapto group (hereinafter, also referred to as "specific reactive polysiloxane") and at least one of a (meth) acrylate, and which has no polymerizable group and has a weight average molecular weight (Mw) of 20000 or more and 400000 or less.

The weight average molecular weight (Mw) of the specific (meth) acrylic acid-modified polyorganosiloxane is 20000 to 400000.

In the present disclosure, the specific (meth) acrylic-modified polyorganosiloxane has Mw of 20000 or more, and thus the abrasion resistance of an image can be improved. From the viewpoint of the abrasion resistance of the image, the Mw of the specific (meth) acrylic acid-modified polyorganosiloxane is more preferably 30000 or more, and particularly preferably 50000 or more.

In the present disclosure, when the Mw of the specific (meth) acrylic acid-modified polyorganosiloxane is 400000 or less, the IJ ejection stability of the liquid composition can be further improved. From the viewpoint of IJ ejection stability, the Mw of the specific (meth) acrylic acid-modified polyorganosiloxane is more preferably 300000 or less, and particularly preferably 200000 or less.

The graft copolymer of the specific reactive polysiloxane and the (meth) acrylate is particularly preferable as the specific (meth) acrylic acid-modified polyorganosiloxane.

As described above, the content (total content in the case of 2 or more types) of the specific (meth) acrylic acid-modified polyorganosiloxane in the liquid composition of the present disclosure is 0.1 mass% or more and 5.0 mass% or less.

By setting the content to 0.1 mass% or more, the abrasion resistance of the image can be improved. From the viewpoint of further improving the abrasion resistance of the image, the content is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more.

By setting the content to 5.0 mass% or less, the IJ ejection stability of the liquid composition can be improved. From the viewpoint of further improving the IJ ejection stability of the liquid composition, the content is preferably 4.0% by mass or less, and more preferably 3.0% by mass or less.

The copolymerization mass ratio of the specific reactive polysiloxane to the (meth) acrylate in the specific (meth) acrylic acid-modified polyorganosiloxane [ (meth) acrylate/specific reactive polysiloxane ] is preferably 0.5 to 10.0, more preferably 1.0 to 5.0, still more preferably 2.0 to 4.0, and particularly preferably 2.0 to 3.0.

The specific reactive polysiloxane (i.e., the reactive polysiloxane having at least one of a polymerizable group and a mercapto group) used to form the specific (meth) acrylic-modified polyorganosiloxane may be only 1 type, or may be 2 or more types.

The specific reactive polysiloxane is preferably at least one compound represented by the following formula (I).

[ chemical formula 3]

In the formulae (I) and (Z), R¹～R⁶The number of carbon atoms of the hydrocarbon group having 1 to 20 carbon atoms in the group (A) is preferably 1 to 10, more preferably 1 to 6. In addition, onThe hydrocarbon group may be a linear hydrocarbon group, a branched hydrocarbon group, or a cyclic hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group.

In the formulae (I) and (Z), for R¹～R⁶In (3), a preferable mode of the halogenated hydrocarbon group having 1 to 20 carbon atoms is that R is substituted with at least 1 halogen atom¹～R⁶The preferable mode of the hydrocarbon group having 1 to 20 carbon atoms in (A) is the same.

The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom, and particularly preferably a fluorine atom or a chlorine atom.

In the formulae (I) and (Z), R¹～R⁶The carbon number of the hydrocarbyloxy group having 1 to 20 carbon atoms in the group (A) is preferably 1 to 10, more preferably 1 to 6. The hydrocarbyloxy group may be a linear hydrocarbyloxy group, a branched hydrocarbyloxy group, or a cyclic hydrocarbyloxy group. The hydrocarbyloxy group is preferably an aliphatic hydrocarbyloxy group, and more preferably an alkoxy group.

In the formulae (I) and (Z), as Y and R⁶The polymerizable group in (2) is preferably a group having an ethylenic double bond, and more preferably a group having at least one of a vinyl group and a 1-methylvinyl group.

The polymerizable group is particularly preferably a (meth) acryloyl group from the viewpoint of polymerization reactivity and hardness of the film to be formed.

In the formulae (I) and (Z), Y and R⁶The number of carbon atoms of the organic group having at least one of a polymerizable group and a mercapto group in (1) is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6.

As Y and R⁶The organic group having at least one of a polymerizable group and a mercapto group in (1) is particularly preferably a mercaptoalkyl group having 1 to 20 carbon atoms.

In the formula (I), m represents an integer of 1 to 10000, and m is preferably an integer of 2 to 1000, more preferably an integer of 3 to 500, and particularly preferably an integer of 5 to 100.

In the formula (I), n represents an integer of 1 or more, and as n, an integer of 2 to 1000 is preferable, an integer of 3 to 500 is more preferable, and an integer of 5 to 100 is particularly preferable.

Wherein m and n in the formula (I) can be adjusted as appropriate so that the Mw of the specific (meth) acrylic acid-modified polyorganosiloxane is 20000 or more and 400000 or less.

In the formula (I), the ratio [ m/n ] of m to n is preferably 1 to 10000, more preferably 1 to 1000, and particularly preferably 1 to 100.

Even when a mixture of 2 or more compounds represented by the formula (I) is used for forming a specific (meth) acrylic-modified polyorganosiloxane, the ratio [ m/n ] of m to n in the entire mixture is preferably 1 to 10000, more preferably 1 to 1000, and particularly preferably 1 to 100.

The compound represented by the formula (I) is particularly preferably a mercaptoalkyl group wherein Y in the formula (I) is a C1-20 (more preferably 1-10, further preferably 1-3) mercapto group, and R in the formula (Z)⁶A hydrocarbon group having 1 to 20 (more preferably 1 to 10, further preferably 1 to 3) carbon atoms, a halogenated hydrocarbon group having 1 to 20 (more preferably 1 to 10, further preferably 1 to 3) carbon atoms, a hydrocarbyloxy group having 1 to 20 (more preferably 1 to 10, further preferably 1 to 3) carbon atoms, or a mercaptoalkyl group having 1 to 20 (more preferably 1 to 10, further preferably 1 to 3) carbon atoms.

The number of (meth) acrylates used to form the specific (meth) acrylic-modified polyorganosiloxane may be only 1, or may be 2 or more.

The (meth) acrylate is preferably at least one compound represented by the following formula (II).

[ chemical formula 4]

In the formula (II), R⁷Represents a hydrogen atom or a methyl group, R⁸Represents an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a C3 alkyl group20 cycloalkyl groups or aryl groups having 6 to 20 carbon atoms.

R in the formula (II)⁸The alkyl group having 1 to 20 carbon atoms in the group (A) may be a straight-chain alkyl group or a branched-chain alkyl group.

The alkyl group having 1 to 20 carbon atoms may be an unsubstituted straight-chain alkyl group or a branched-chain alkyl group, may be a straight-chain alkyl group or a branched-chain alkyl group substituted with a cycloalkyl group, or may be a straight-chain alkyl group or a branched-chain alkyl group (i.e., an aralkyl group) substituted with an aryl group, as long as the carbon number is 1 to 20.

The alkyl group having 1 to 20 carbon atoms preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.

For R in the formula (II)⁸Wherein the alkoxyalkyl group having 2 to 20 carbon atoms is substituted with an alkoxy group except that the total carbon atoms of the entire alkoxyalkyl group is 2 to 20, and R in the formula (II)⁸The alkyl group having 1 to 20 carbon atoms has the same meaning, and the preferable embodiment is the same.

The number of carbon atoms of the alkoxyalkyl group having 2 to 20 carbon atoms (the total number of carbon atoms of the entire alkoxyalkyl group) is preferably 2 to 12, more preferably 2 to 10, and particularly preferably 2 to 6.

For R in the formula (II)⁸Wherein the hydroxyalkyl group having 1 to 20 carbon atoms is substituted with a hydroxy group, and R in the formula (II)⁸The alkyl group having 1 to 20 carbon atoms has the same meaning, and the preferable embodiment is the same.

R in the formula (II)⁸The cycloalkyl group having 3 to 20 carbon atoms in (A) may be an unsubstituted cycloalkyl group or a cycloalkyl group substituted with a straight-chain alkyl group or a branched-chain alkyl group.

The cycloalkyl group having 3 to 20 carbon atoms preferably has 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 6 carbon atoms.

R in the formula (II)⁸The aryl group having 6 to 20 carbon atoms in (A) may be an unsubstituted aryl group or an aryl group substituted with an alkyl group.

The number of carbon atoms of the aryl group having 6 to 20 carbon atoms is preferably 6 to 12.

The liquid composition of the present disclosure may contain a polyorganosiloxane other than the specific (meth) acrylic acid-modified polyorganosiloxane within a range not to impair the effects of the liquid composition of the present disclosure.

For example, the liquid composition of the present disclosure may contain a (meth) acrylic-modified polyorganosiloxane having a polymerizable group. The (meth) acrylic-modified polyorganosiloxane having a polymerizable group is classified into a specific polymerizable compound described later or another polymerizable compound described later.

< organic solvent >

The liquid compositions of the present disclosure contain at least one organic solvent.

As described above, the content of the organic solvent in the liquid composition of the present disclosure is 40 mass% or more and 80 mass% or less with respect to the total amount of the liquid composition.

By setting the content of the organic solvent to 40% by mass or more, the IJ ejection stability of the liquid composition can be improved. From the viewpoint of further improving the IJ ejection stability of the liquid composition, the content of the organic solvent is more preferably 50% by mass or more, and particularly preferably 60% by mass or more.

On the other hand, by setting the content of the organic solvent to 80% by mass or less, the abrasion resistance of the image can be improved.

The organic solvent is not particularly limited, and may be selected from any organic solvents generally used in the printing industry.

Examples of the organic solvent include: glycol ethers, glycol ether esters, alcohols, ketones, esters, pyrrolidones, and the like.

Examples of the glycol ether include: ethylene glycol monomethyl ether, diethylene glycol diethyl ether, triethylene glycol monobutyl ether, and the like.

Examples of the ketone include methyl ethyl ketone.

Examples of the ester include: 3-methoxybutyl acetate, gamma-butyrolactone, and the like.

Examples of the pyrrolidone include N-methyl-2-pyrrolidone and the like.

Among them, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, 3-methoxybutyl acetate, and γ -butyrolactone are preferable.

The boiling point of the organic solvent is preferably 75 ℃ or higher and 300 ℃ or lower, more preferably 100 ℃ or higher and 250 ℃ or lower, still more preferably 150 ℃ or higher and 250 ℃ or lower, and particularly preferably 150 ℃ or higher and 200 ℃ or lower.

When the boiling point of the organic solvent is 75 ℃ or higher, the adhesion of the image is further improved. On the other hand, when the boiling point is 300 ℃ or less, bleeding of the image is further suppressed.

< polymerizable Compound having a weight-average molecular weight of 1000 to 30000 >

The liquid composition of the present disclosure contains at least one polymerizable compound (hereinafter, also referred to as "specific polymerizable compound") having a weight average molecular weight of 1000 or more and 30000 or less.

The preferable range of the content of the specific polymerizable compound in the liquid composition is as described above.

The polymerizable compound is a compound having a polymerizable group.

Examples of the polymerizable group include a radical polymerizable group and a cation polymerizable group, and a radical polymerizable group is preferable.

The radical polymerizable group is preferably a group containing an ethylenic double bond, more preferably a group containing at least one of a vinyl group and a 1-methylvinyl group, and particularly preferably a (meth) acryloyl group.

Examples of the cationically polymerizable group include an epoxy group.

The specific polymerizable compound has a weight average molecular weight of 1000 or more and 30000 or less.

By making the weight average molecular weight of the specific polymerizable compound 1000 or more, the flexibility of the image can be improved.

By setting the weight average molecular weight of the specific polymerizable compound to 30000 or less, the IJ ejection stability and the abrasion resistance of an image can be improved.

The weight average molecular weight of the specific polymerizable compound is preferably 1000 or more and 20000 or less, more preferably 1000 or more and 15000 or less, further preferably 1000 or more and 10000 or less, and particularly preferably 1500 or more and 10000 or less.

As the specific polymerizable compound, a 2-to 6-functional polymerizable compound can be used.

The 2-to 6-functional polymerizable compounds herein mean compounds each having 2 to 6 polymerizable groups in one molecule.

The specific polymerizable compound is preferably a 2-to 4-functional polymerizable compound, more preferably a 2-to 3-functional polymerizable compound, and particularly preferably a 2-functional polymerizable compound, from the viewpoint of further improving the flexibility of the image.

The specific polymerizable compound is preferably an acrylate compound such as urethane acrylate, bisphenol a epoxy acrylate, or epoxy novolac acrylate, and particularly preferably urethane acrylate.

< other polymerizable Compound >

The liquid composition of the present disclosure may contain at least one of a polymerizable compound having a weight average molecular weight of less than 1000 (hereinafter, also referred to as "polymerizable monomer" or "monomer") and a polymerizable compound having a weight average molecular weight of more than 30000, other than the specific polymerizable compound, within a range not to impair the effects of the liquid composition of the present disclosure.

Examples of the polymerizable monomer include:

monofunctional (meth) acrylate monomers such as phenoxyethyl acrylate (PEA), Cyclic Trimethylolpropane Formal Acrylate (CTFA), isobornyl acrylate (IBOA), tetrahydrofurfuryl acrylate (THFA), 2- (2-ethoxyethoxy) ethyl acrylate, octadecyl acrylate (ODA), tridecyl acrylate (TDA), isodecyl acrylate (IDA), lauryl acrylate, and the like;

multifunctional (meth) acrylate monomers such as hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylates (e.g., tetraethylene glycol diacrylate), dipropylene glycol diacrylate, tri (propylene glycol) triacrylate, neopentyl glycol diacrylate, bis (pentaerythritol) hexaacrylate, ethoxylated or propoxylated ethylene glycol diacrylates (e.g., propoxylated neopentyl glycol diacrylate), ethoxylated or propoxylated polyol polyacrylates (e.g., ethoxylated trimethylolpropane triacrylate), mixtures of ethoxylated or propoxylated ethylene glycol diacrylate and ethoxylated or propoxylated polyol polyacrylates;

vinyl ether monomers such as triethylene glycol divinyl ether, diethylene glycol divinyl ether, 1, 4-cyclohexanedimethanol divinyl ether, and ethylene glycol monovinyl ether;

n-vinyl amides such as N-vinyl caprolactam (NVC) and N-vinyl pyrrolidone (NVP);

and N- (meth) acrylamide such as N-Acryloylmorpholine (ACMO).

Among these, from the viewpoint of further improving the flexibility of an image, the content of the polymerizable monomer in the liquid composition of the present disclosure is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 1% by mass or less, relative to the total amount of the liquid composition. The content of the polymerizable monomer in the liquid composition of the present disclosure may also be 0 mass% (that is, the liquid composition of the present disclosure may not contain the polymerizable monomer).

From the same viewpoint (i.e., the viewpoint of further improving the flexibility of an image), the proportion of the specific polymerizable compound of the present disclosure in the total amount of the polymerizable compounds contained in the liquid composition is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. The specific polymerizable compound of the present disclosure may be contained in the liquid composition in a proportion of 100% by mass of the total amount of the polymerizable compounds contained in the liquid composition.

< photopolymerization initiator >

The liquid composition of the present disclosure contains at least one photopolymerization initiator.

Examples of the photopolymerization initiator include: radical photopolymerization initiators such as benzophenone, 1-hydroxycyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-benzyl-2-dimethylamino- (4-morpholinophenyl) butan-1-one, isopropylthioxanthone, benzyl dimethyl ketal, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, bis (2, 6-dimethylbenzoyl) -2,4, 4-trimethylpentylphosphine oxide, and the like.

These free radical photopolymerization initiators are well known. Commercially available products of these radical photopolymerization initiators include: IRGACURE (registered trademark), Darocur (registered trademark), LUCIRIN (registered trademark) (manufactured by BASF corporation, supra), and the like.

In addition, when the specific polymerizable compound is a compound having a cationically polymerizable group, a cationic photopolymerization initiator may be used as the photopolymerization initiator. As the cationic photopolymerization initiator, for example, a photopolymerization initiator based on sulfonium or iodonium salts can be used. Examples of commercially available photopolymerization initiators based on sulfonium or iodonium salts include: rhodorsil PI 2074 from Rhodia; MC AA, MC BB, MC CC PF, MC SD of Siber Hegner company; UV9380c from Alfa Chemicals; uvacure 1590 from UCB Chemicals; and Escapure 1064 from Lamberti spa, Inc.

The content of the photopolymerization initiator in the liquid composition of the present disclosure is preferably 1 to 20% by mass, and more preferably 4 to 10% by mass, with respect to the total amount of the liquid composition.

< coloring agent >

The liquid compositions of the present disclosure may also contain at least one colorant.

As described above, the manner in which the liquid composition contains the colorant is suitable for the case where the liquid composition is used as a coloring ink.

When the liquid composition of the present disclosure contains a colorant, the content of the colorant is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more, relative to the total amount of the liquid composition.

When the liquid composition of the present disclosure contains a colorant, the upper limit of the content of the colorant is preferably 20 mass%, more preferably 10 mass%, still more preferably 8 mass%, and particularly preferably 5 mass% with respect to the total amount of the liquid composition.

The colorant is not particularly limited, and may be a pigment or a dye.

The pigment is not particularly limited and may be appropriately selected depending on the purpose. The pigment may be dissolved or dispersed in the liquid composition.

The pigment may be either an organic pigment or an inorganic pigment, or both an organic pigment and an inorganic pigment may be used.

Examples of the organic pigment include: polycyclic pigments such as azo lakes, azo pigments, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye lakes such as basic dye lakes and acid dye lakes; nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments.

Examples of the inorganic pigment include: titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow and carbon black.

As the colorant, for example, an organic pigment or an inorganic pigment of the following numbers described in the color index can be used.

Examples of the blue pigment and the cyan pigment include: pigment Blue 1, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, 60;

examples of the green pigment include: pigment Green 7, 26, 36, 50;

examples of the red pigment and the magenta pigment include: pigment Red 3, 5, 9, 19, 22, 31, 38, 42, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:2, 58:4, 63:1, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36;

examples of the yellow pigment include: pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 120, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193;

examples of the black pigment include: segment Black 7, 28, 26;

examples of the white pigment include: pigment White 6, 18, 21.

In addition, even pigments not described in the color index can be used appropriately according to the purpose. For example, a pigment surface-treated with a surfactant, a polymer dispersant, or the like, a grafted carbon, or the like may be further used.

Examples of the polymer dispersant include: polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, polyether esters, and the like.

As the polymer dispersant, commercially available products can be used, and examples thereof include: the dispersant may be any of the compounds of the classes of dispersant BYK-101, Disper BYK-102, Disper BYK-103, Disper BYK-106, Disper BYK-111, Disper BYK-161, Disper BYK-162, Disper BYK-163, Disper BYK-164, Disper BYK-166, Disper BYK-167, Disper BYK-168, Disper BYK-170, Disper BYK-171, Disper BYK-174, Disper BYK-182 (BYK Chemie), EFKA4010, EFKA4046, EFKA4080, EFKA5010, EFKA5207, EFKA5244, EFKA6745, EFKA6750, EFKA 14, EF74745, EFKA7462, EFKA7500, EF7570, EF7575, EFKA 9180 (EFKA 759180), disperKA 9117, and Noperse Aid 7, and Noper Aid, such as molecular weight-index No. 7, EFKA 918, and Noper Aid; various SOLSPERSE dispersants (manufactured by Avecia corporation), such as SOLSPERSE (Solsperse)3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, 32000, 36000, 39000, 41000, and 71000; ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by ADEKA CORPORATION), Ionet (registered trademark) S-20 (manufactured by Sanyo chemical industries Co., Ltd.), DISPARLON KS-860, 873SN, 874 (polymeric dispersant), 2150# (aliphatic polycarboxylic acid), 7004# (polyether ester type) ".

In the pigment surface-treated with the polymeric dispersant, the content ratio of the polymeric dispersant to the pigment (polymeric dispersant: pigment) is preferably 1:1 to 1:10, more preferably 1:1 to 1:5, and still more preferably 1:2 to 1: 3.

As the colorant, commercially available products can be used. Examples of commercially available products include: paliotol (manufactured by BASF), Cinqasia, Irgalite (manufactured by Ciba Speciality Chemicals) and Hostaperm (manufactured by Clariant UK).

Among these colorants, phthalocyanine pigments such as pigment blue 15:4 are preferable as the cyan pigment. The yellow pigment is preferably an azo pigment such as pigment yellow 120, pigment yellow 151, or pigment yellow 155. Preferred MAGENTA pigments include pigment violet 19, and quinacridone pigments such as mixed crystal quinacridones (e.g., Cinqasia MAGENTA L4540). The black pigment is preferably a carbon black pigment such as pigment black 7.

The volume average particle diameter of the colorant is not particularly limited, but is preferably less than 8 μm, more preferably less than 5 μm, still more preferably less than 1 μm, and particularly preferably less than 0.5 μm, from the viewpoint of ink ejection property. The lower limit of the volume average particle diameter of the colorant is not particularly limited, but is preferably 0.001 μm or more, and more preferably 0.01 μm or more, from the viewpoint of colorability and light fastness.

The volume average particle diameter can be measured by a laser diffraction particle size distribution analyzer (for example, Mastersizer 2000 manufactured by Malvern, laser diffraction/scattering particle size distribution analyzer LA-920 manufactured by horiba, Ltd.).

< other ingredients >

The liquid composition of the present disclosure may contain other components than those described above as necessary.

Examples of the other components include: surfactant, polymerization inhibitor, sensitizer, ultraviolet absorbent, antioxidant, fading inhibitor, conductive salt and alkaline compound.

Examples of the surfactant include those described in Japanese patent application laid-open Nos. 62-173463 and 62-183457.

Examples of the surfactant include: anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, and fatty acid salts; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylallyl ethers, acetylene glycols, polyoxyethylene-polyoxypropylene block copolymers, and silicones; cationic surfactants such as alkylamine salts and quaternary ammonium salts.

The content of the surfactant in the liquid composition of the present disclosure may be appropriately selected depending on the purpose of use, and is preferably 0.0001 to 1% by mass, and more preferably 0.01 to 1% by mass, with respect to the total amount of the liquid composition.

Examples of the polymerization inhibitor include: p-methoxyphenol, quinones (e.g., hydroquinone, benzoquinone, methoxybenzoquinone, etc.), phenothiazine, orthophenyldiols, alkylphenols (e.g., dibutylhydroxytoluene (BHT)), alkylbisphenols, zinc dimethyldithiocarbamate, copper dibutyldithiocarbamate, copper salicylate, thiodipropionate, mercaptobenzimidazole, phosphates, 2,6, 6-tetramethylpiperidin-1-oxyl (TEMPO), 2,6, 6-tetramethyl-4-hydroxypiperidin-1-oxyl (TEMPOL), cupferrol Al, tris (N-nitroso-N-phenylhydroxylamine) aluminum salts, and the like.

Among these polymerization inhibitors, at least one selected from the group consisting of p-methoxyphenol, catechol, quinones, alkylphenols, TEMPO, TEMPOL, cupferrol Al and tris (N-nitroso-N-phenylhydroxylamine) aluminum salt is preferable, and at least one selected from the group consisting of p-methoxyphenol, hydroquinone, benzoquinone, BHT, TEMPO, TEMPOL, cupferrol Al and tris (N-nitroso-N-phenylhydroxylamine) aluminum salt is more preferable.

The content of the polymerization inhibitor in the liquid composition of the present disclosure may be appropriately selected depending on the purpose of use, and is preferably 0.0001 to 1% by mass, and more preferably 0.01 to 1% by mass, based on the total amount of the liquid composition.

< preferred Properties of liquid composition >

The surface tension of the coloring ink is preferably 18mN/m or more and 40mN/m or less, more preferably 22mN/m or more and 35mN/m or less, and still more preferably 25mN/m or more and 30mN/m or less at 25 ℃.

The Surface tension can be measured at 25 ℃ by using an Automatic Surface Tensiometer CBVP-Z (Kyowa interface science Co., Ltd.).

The viscosity of the liquid composition is preferably 200 mPas or less, more preferably 100 mPas or less at 25 ℃. More preferably 25 mPas or less, still more preferably 10 mPas or less, and particularly preferably 7 mPas or less.

The viscosity of the liquid composition is preferably 2 mPas or more, more preferably 4 mPas or more, and particularly preferably 5 mPas or more at 25 ℃.

The viscosity of the liquid composition was measured by using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD.).

[ recorded Medium ]

Use of the liquid composition of the present disclosure for forming an image on a recording medium by an ink jet method.

As described above, the liquid composition of the present disclosure can form an image having excellent abrasion resistance and bendability. Therefore, the liquid composition of the present disclosure is particularly suitable for the use of ink jet recording on a soft base material as a recording medium, for example, the use of decorative printing by ink jet recording on leather products (for example, vehicle seats, bags, shoes, purses, etc.). However, the liquid composition of the present disclosure is not limited to the above-described application, and may be used for general inkjet recording performed on a general recording medium such as paper.

As described above, the recording medium is preferably a flexible substrate. Specific examples of the soft base include: leather, cloth, polymer films, and the like. Among them, leather is preferable.

Examples of the leather include: natural leather (also referred to as "genuine leather"), synthetic leather (e.g., PVC (polyvinyl chloride) leather, PU (polyurethane) leather), and the like. For leather, see paragraphs 0163 to 0165 of Japanese patent laid-open publication No. 2009-058750, for example.

[ ink jet recording method ]

As described previously, the liquid composition of the present disclosure can be used as a coloring ink or a colorless ink (e.g., a topcoat liquid) in inkjet recording.

Hereinafter, an embodiment of an inkjet recording method using the liquid composition of the present disclosure will be described, but the present invention is not limited to the following embodiment.

The inkjet recording method of the present embodiment includes the steps of: a discharge step of forming an image on a recording medium by discharging the liquid composition of the present disclosure from an inkjet head; a heating step of removing at least a part of the organic solvent contained in the image by heating the image formed on the recording medium; and a curing step of curing the image by irradiating the heated image with an active energy ray.

The inkjet recording method of the present embodiment may have other steps as necessary.

By the inkjet recording method of the present embodiment, a cured image (hereinafter, also referred to as "cured image") can be formed on a recording medium. The image concept described herein includes, of course, a solid image.

The liquid composition of the present disclosure has excellent ejection stability (IJ ejection stability) when ejected from an inkjet head in the ejection step. The formed cured image is excellent in abrasion resistance and bendability.

The range of the inkjet recording method of the present embodiment includes method a: in the ejection step, the liquid composition of the present disclosure in a form containing a colorant is ejected onto a recording medium.

According to the method A, a colored image having excellent abrasion resistance and bendability can be formed.

The ink jet recording method of the present embodiment further includes a method B: in the ejection step, the liquid composition of the present disclosure (hereinafter, also referred to as "colorless ink") is ejected onto a colored image of a recording medium on which a colored image is formed, in such a manner that the content of the colorant is less than 0.1% by mass.

According to the method B, the colored image can be covered with the top-coat film obtained by curing the liquid composition. That is, a colored image covered with a top-coat film (hereinafter, also referred to as "colored image with a top-coat film") can be obtained.

The colored image in the method B is not particularly limited, and for example, a colored image formed by an ink jet method is exemplified. The liquid composition of the present disclosure may be used in a form containing a colorant, or a coloring ink other than the liquid composition of the present disclosure may be used for forming the colored image.

The coloring ink other than the liquid composition of the present disclosure may be a photocurable coloring ink (i.e., a coloring ink containing a polymerizable compound) or a non-photocurable coloring ink (i.e., a coloring ink containing no polymerizable compound) as long as it contains at least a colorant.

< Ejection step >

The ejection step in the inkjet recording method of the present embodiment is a step of forming an image by ejecting the liquid composition of the present disclosure from the inkjet head onto a recording medium.

The discharge method of the liquid composition discharged from the ink jet head is not particularly limited, and known methods such as: a charge control method for ejecting ink by using electrostatic induction force; a drop on demand (pressure pulse) method using a vibration pressure of a piezoelectric element; a sound control ink jet method of converting an electric signal into a sound beam and irradiating the sound beam on the ink and ejecting the ink by using radiation pressure; a thermal inkjet (registered trademark) system in which ink is heated to form bubbles and the pressure generated is used.

< heating Process >

The heating step in the inkjet recording method of the present embodiment is a step of removing at least a part of the organic solvent contained in the image by heating the image formed on the recording medium.

In addition, from the viewpoint of suppressing bleeding of an image and improving the adhesion of an image, the heating in the heating step is preferably performed while keeping the surface temperature of the recording medium at 40 ℃ or higher and 100 ℃ or lower (more preferably, 40 ℃ or higher and 80 ℃ or lower, and still more preferably, 50 ℃ or higher and 70 ℃ or lower).

From the same viewpoint as described above, the heating time in the heating step is preferably 1 second or more, more preferably 5 seconds or more, and particularly preferably 8 seconds or more.

The upper limit of the heating time is not particularly limited, but the upper limit is preferably 60 seconds, more preferably 30 seconds, and particularly preferably 20 seconds.

< curing Process >

The curing step in the inkjet recording method of the present embodiment is a step of irradiating the heated image with an active energy ray to cure the image.

By this step, the image on the recording medium can be cured to form a cured image excellent in abrasion resistance and bendability.

As the active energy ray, α -ray, γ -ray, electron beam, X-ray, ultraviolet ray, visible light, infrared ray, or the like can be used. When a sensitizer is used, the peak wavelength of the active energy ray depends on the absorption characteristics of the sensitizer, and is, for example, preferably 200nm to 600nm, more preferably 300nm to 450nm, and still more preferably 350nm to 420 nm.

Preferably, the exposure surface illuminance is preferably 10mJ/cm²～10000mJ/cm²More preferably 100mJ/cm²～5000mJ/cm²Allowing it to cure.

As the active energy source, a general active energy source such as a mercury lamp, a metal halide lamp, a gas laser, a solid laser, a GaN semiconductor ultraviolet light emitting device (light emitting diode (LED), Laser Diode (LD), or the like) can be used without particular limitation.

As an example of the LED, a violet LED having a main emission spectrum wavelength of 365nm and 420nm is available from Nissan chemical Co. In the case where a shorter wavelength is further required, as the LED, an LED capable of emitting active energy rays having a wavelength center between 300nm and 370nm disclosed in specification of U.S. patent No. 6,084,250 can be exemplified. In addition, other ultraviolet LEDs are available that can illuminate radiation in different ultraviolet bands.

The irradiation time of the active energy ray is preferably 0.01 to 120 seconds, more preferably 0.1 to 90 seconds.

Specific examples of the active energy ray irradiation include: a shuttle system in which an active energy ray irradiation device is provided in a short serial head and irradiation is performed while the head is scanned in the width direction of a recording medium; a single pass system in which the active energy ray irradiation devices are arranged corresponding to the entire length of one side of the recording medium.

The irradiation conditions and the basic irradiation method of the active energy ray can be found in, for example, a publicly known document such as Japanese patent application laid-open No. 60-132767.

The irradiation with the active energy ray is preferably performed after leaving for a certain period of time (preferably 0.01 to 0.5 seconds, more preferably 0.01 to 0.3 seconds, and further preferably 0.01 to 0.15 seconds) after the completion of the heating step.

Further, the curing of the liquid composition may be accomplished by using another light source without driving. International publication No. 99/54415 discloses a method using an optical fiber and a method of irradiating a recording portion with ultraviolet rays by aligning a calibrated light source with a mirror surface provided on a side surface of a head unit, and this curing method can be applied to the inkjet recording method of the present embodiment.

The inkjet recording method of the present embodiment can be implemented using a known inkjet recording apparatus.

Examples of recording methods of the ink jet recording apparatus include: a shuttle system that uses a short serial head and performs recording while scanning the head in the width direction of a recording medium; a line type system (single-pass system) using a line type inkjet head in which recording elements are arranged corresponding to the entire length of one side of a recording medium.

In the ink jet recording method of the present embodiment, an ink jet recording apparatus of either shuttle type or line type can be used. As a shuttle type ink jet recording apparatus, for example, japanese patent application laid-open No. 2010-280828 can be cited.

[ examples ]

The present invention will be described in more detail with reference to the following examples. The scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part(s)" and "%" are based on mass.

[ production of a specific (meth) acrylic acid-modified polyorganosiloxane ]

Polymers 1 to 3 are produced as specific examples of the (meth) acrylic acid-modified polyorganosiloxane. The details are described below.

< production of Polymer 1 >

(preparation of emulsifier A)

The components having the following composition were mixed, stirred, and then treated with a homogenizer (12000rpm, the same shall apply hereinafter) to obtain an emulsifier A.

Composition of emulsifier A-

Octamethylcyclotetrasiloxane … 1500 parts

… 98.4.4 parts of 3-mercaptopropyltrimethoxysilane (KBM-803, product of shin-Etsu chemical Co., Ltd.)

… 1500 parts of ultrapure water

… 100 parts of sodium lauryl sulfate

… 100 parts of dodecyl benzene sulfonic acid

(preparation of emulsifier B)

Heating the emulsifier A at 70 deg.C for 12 hr, cooling to 25 deg.C, and aging for 24 hr. Then, sodium carbonate was added to the aged emulsifier to adjust the pH to 7, followed by blowing nitrogen gas for 4 hours. The volatile siloxane is then distilled off from the emulsifier by means of steam distillation.

The emulsifier B having a solid content concentration of 45% was obtained by adding ultrapure water to the emulsifier remaining after the above distillation removal.

As a result of analysis by infrared absorption spectroscopy and NMR spectroscopy, it was estimated that the emulsifier B contained a mixture of the compound (I-1) having the following structure (i.e., a mixture having m/n of 10.1).

Further, it is considered that the emulsifier B contains the compound (I-1) having m of 1 to 10000 and n of 1 or more, based on the weight average molecular weight (60000) of the polymer 1 described later.

[ chemical formula 5]

(preparation of emulsifier C)

After filling a reaction vessel (nitrogen atmosphere) with a liquid of group 1 having the following composition, the temperature was maintained at 10 ℃. To this was slowly added a mixture of group 2 consisting of the following. Thereafter, a mixture of group 3 having the following composition was added dropwise thereto over 5 hours. After completion of the dropwise addition of the mixture of group 3, the resulting mixture was stirred for 2 hours.

Then, ultrapure water was added to the mixture after stirring for 2 hours, thereby obtaining emulsifier C having a solid content concentration of 25%.

Composition of the liquid of group-1-

Emulsifier B … 477 parts

… 1400 portions of pure water

Composition of the mixture of group-2

… 1.0.0 parts of tert-butyl hydroperoxide

0.5 portion of L-ascorbic acid … 0.5

0.002 part of ferrous sulfate heptahydrate … 0.002

Composition of the mixture of group-3

… 147 parts of ethyl acrylate

… 343 parts of methyl methacrylate

… 10 parts of 2-hydroxyethyl methacrylate

(production of Polymer 1)

A mixture P1 having the following composition was stirred while keeping the temperature at 60 ℃ to precipitate a solid. The precipitated solid was repeatedly filtered and washed with water, and then dried at 70 ℃ to obtain polymer 1.

Composition of the mixture P1

Emulsifier C … 1000 parts

… 92 portions of sodium sulfate

… 470 parts of pure water

The volume average primary particle diameter (hereinafter, also simply referred to as "particle diameter") of the obtained polymer 1 was measured using a laser diffraction/scattering particle size distribution measuring apparatus (LA920, manufactured by horiba, Ltd.) and tripropylene glycol methyl ether as a measuring solvent, and the particle diameter was 0.1. mu.m.

The weight average molecular weight (Mw) of the obtained polymer 1 was measured by the aforementioned method using GPC, and the Mw was 60000.

The particle diameter and Mw of the specific (meth) acrylic-modified polyorganosiloxane other than the polymer 1, which will be described below, are measured by the same method as that for the polymer 1.

< production of polymers 2 and 3 >

In the production of the polymer 1, the number of revolutions of the homogenizer, the concentration of sodium lauryl sulfate, and the concentration of dodecylbenzenesulfonic acid were changed at the stage of obtaining the emulsifier a, thereby obtaining a polymer 2 having a particle size of 0.2 μm and an Mw of 100000 and a polymer 3 having a particle size of 0.3 μm and an Mw of 150000, respectively.

It is considered that the weight average molecular weights (100000 and 150000) of these polymers 2 and 3 are such that the compound (I-1) described above, in which m is 1 to 10000 and n is 1 or more, is contained in the emulsifier B in the intermediate stage for obtaining each polymer.

Further, CHALINE (registered trademark) R175S (manufactured by Nissan chemical industries, Ltd.) was prepared as a specific (meth) acrylic-modified polyorganosiloxane.

CHALINE (registered trademark) R175S had a particle size of 0.2 μm and Mw of 100000.

The polymers 1 to 3 and CHALINE R175S are specific examples of the (meth) acrylic acid-modified polyorganosiloxane.

[ preparation of pigment Dispersion ]

The components other than the pigments shown in table 1 below were mixed so as to have the compositions shown in table 1, and stirred by a stirrer of SILVERSON corporation under conditions of 2,000 rpm to 3,000 rpm and 10 minutes to 15 minutes, to obtain a uniform dispersant diluent. To this dispersant diluent, each pigment was added in the kind and amount shown in table 1, and further stirred by a stirrer under conditions of 2,000 rpm to 3,000 rpm, and 10 minutes to 20 minutes, to obtain 500 parts of a uniform predispersion.

Thereafter, each of the obtained predispersions was subjected to a dispersion treatment using a circulation type bead mill (SL-012C1) manufactured by Dispermat to obtain a pigment dispersion of each color. The above-mentioned circulation type bead mill was charged with 200 parts of zirconia beads having a diameter of 0.65mm, and the dispersion treatment was carried out under conditions of a peripheral speed of 15m/s and a dispersion time of 1 to 6 hours.

[ Table 1]

The details of the ingredients in table 1 are as follows.

PB15:4 … C.I. pigment blue 15:4, BASF corporation, HELIGOEN BULE D7110F

Mixed quinacridone … BASF, CINQUASIA MAGENTA L4540

PY155 … C.I. pigment YELLOW 155, Clarina, INK JET YELLOW 4GC

Carbon Black … CABOT, MOGUL E

Sol32000 … Luburizol, SOLSPERSE 32000

DEGDE … Tokyo Chemicals Co., Ltd, diethylene glycol diethyl ether

[ example 1]

< preparation of pigmented inks >

Each component having the composition shown in table 2 below was mixed and stirred by a stirrer manufactured by SILVERSON under conditions of 2,000 rpm to 3,000 rpm and 10 minutes to 15 minutes, thereby preparing a coloring ink (cyan ink in example 1) as a liquid composition for an inkjet printer.

< formation of cured image >

An inkjet printer was prepared, which was equipped with an inkjet head CA4 manufactured by TOSHIBA TEC corporation.

The ink jet printer was filled with the coloring ink, and the coloring ink was ejected from the ink jet head heated to 35 ℃ to form a colored layer on a substrate [ PVC leather; a solid image (cyan solid image in example 1) was printed on cuppcino CP-830(YAMAPLAS co., LTD.) ]. At this time, the image density was 1200dpi × 600dpi, and the amount of the coloring ink applied to the substrate was 20g/m²。

Then, the substrate on which the solid image was formed was heated at a substrate temperature of 60 ℃ for 10 seconds using a rubber heater, thereby drying the solid image.

Then, for the solid image after drying, a UV exposure machine was used at 3000mJ/cm²The solid image is cured by irradiating UV (ultraviolet) with the irradiation amount of (1) to obtain a cured image.

In the present specification, "dpi" means dot per inch.

< evaluation >

The cured image and the colored ink were used to evaluate the following. The results are shown in Table 2.

(abrasion resistance A)

The cured image was subjected to abrasion using a chemical vibration tester (Suga tester) for a predetermined number of times while applying a load of 200g to the dried cotton. Meanwhile, the number of times until the damage is visually recognized on the cured image is recorded, and the abrasion resistance of the cured image is evaluated in accordance with the following evaluation criteria (hereinafter referred to as "abrasion resistance a"). Among the following evaluation criteria, 3 points or more were passed.

Abrasion resistance A evaluation criteria

No damage was observed after 5 min 2000.

Injury occurred in more than 1000 and less than 2000 times in 4 minutes.

The 3 points produced lesions more than 500 times and less than 1000 times.

2 min produced lesions more than 100 times and less than 500 times.

1 minute produced lesions less than 100 times.

(flexibility)

The substrate on which the cured image was formed was bent a predetermined number of times using a bending machine (Flexo-Meter, manufactured by Anthemis Seisakusho K.K.). Meanwhile, the number of times until cracks were visually recognized on the cured image was recorded, and the bendability of the cured image was evaluated according to the following evaluation criteria. Among the following evaluation criteria, 3 points or more were passed.

Evaluation criteria for bendability-

No cracks were generated even after 5 min to 20000 cycles.

Cracks were generated in 4 points less than 20000 times and more than 10000 times.

Cracks are generated in 3 minutes of 5000 times or more and less than 10000 times.

Cracks were generated in the 2 min 1000 times or more and less than 5000 times.

Cracks occurred in less than 1000 times for 1 minute.

(drug resistance)

The cured image was subjected to abrasion using a chemical vibration tester (Suga tester) for a predetermined number of times while applying a load of 400g to cotton impregnated with ethanol. Meanwhile, the number of times until the cured image peeled off and the surface of the substrate could be recognized was recorded, and the chemical resistance of the cured image was evaluated according to the following evaluation criteria. Among the following evaluation criteria, 3 points or more were passed.

Evaluation criteria for drug resistance-

The substrate surface could not be identified 5 minutes and 200 times.

The substrate surface can be identified for 4 points more than 100 times and less than 200 times.

The substrate surface can be identified for more than 50 times and less than 100 times in the 3-point.

The substrate surface can be identified more than 10 times and less than 50 times for 2 points.

The score of 1 is less than 10 times the surface of the substrate can be discerned.

(IJ discharge stability)

The solid images were continuously printed on 40 sheets of recording paper (print paper for inkjet; "color" (manufactured by fuji photo film corporation)) having a size of a3 except that the base material was changed to a recording paper (print paper for inkjet;) having a size of a3 under the same conditions as the printing of the solid images, and hereinafter, the 40 sheets of recording paper on which the solid images were printed were visually observed as a "sample", and the number of samples in which nozzle missing (that is, image defects caused by ejection defects of nozzles) could be confirmed in the solid images were examined.

Evaluation criteria for IJ ejection stability-

0 sample capable of confirming nozzle missing spraying in 5 minutes

4-minute sample 1 capable of confirming nozzle missing

2 samples capable of confirming nozzle missing spraying in 3 minutes

2-minute 3 samples capable of confirming nozzle missing

1 minute of 4 or more samples for confirming nozzle blow-out

[ examples 2 to 15, comparative examples 1 to 6 ]

The same operations as in example 1 were performed except that the composition of the coloring ink was changed to the compositions shown in tables 2 and 3 below. The results are shown in tables 2 and 3.

< descriptions in Table 2 to Table 4 >

In tables 2 and 3 and table 4 described later, the numbers shown in the columns of the respective components indicate the amounts (parts by mass) of the components.

The details of each component in tables 2 to 4 are as follows.

- (meth) acrylic acid-modified polyorganosiloxane-

Polymers 1 to 3 … polymers 1 to 3 produced as described above.

R175S … Nissan chemical industries, "CHALINE (registered trademark) R175S" (meth) acrylic acid-modified polyorganosiloxane.

Polyether-modified polyorganosiloxanes

BYK307 … BYK-Chemie Japan company polyether modified polydimethylsiloxane.

Organosilicon polyether acrylates

Tegod 2010 … TEGO (registered trademark) RAD2010 (silicone polyether acrylate) manufactured by Evonik Degussa GmbH. The TEGORAD2010 is not a copolymer of a specific reactive polysiloxane and a (meth) acrylate.

Polymerizable compound-

2-functional urethane acrylate manufactured by CN996 … Sartome company (weight average molecular weight (Mw) ═ 2850)

UA-122P … 2-functional urethane acrylate from kamura chemical industries (Mw 1100)

"Violet light (registered trademark) UV-6630B" (2-functional urethane acrylate, Mw 3000) manufactured by UV-6630B … Nippon synthetic chemical Co., Ltd

"Violet light (registered trademark) UV-3310B" (2-functional urethane acrylate, Mw: 5000, manufactured by UV-3310B … Nippon synthetic chemical Co., Ltd.)

"Violet light (registered trademark) UV-3000B" (2-functional urethane acrylate, Mw 18000, manufactured by UV-3000B … Nippon synthetic chemical Co., Ltd.)

UV-7630B … Nippon synthetic chemical Co., Ltd. "Violet light (registered trademark) UV-7630B" (6-functional urethane acrylate, Mw. 2200)

Photopolymerization initiators

Irg2959 … BASF corporation "IRGACURE 2959" (1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one)

Irg819 … BASF corporation "IRGACURE 819" (bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide)

Surfactants-

BYK331 … BYK-Chemie Japan polyether modified polydimethylsiloxane

Polymerization inhibitors

UV12 … nitroso polymerization inhibitor, tris (N-nitroso-N-phenylhydroxylamine) aluminum salt, available from Kromachem corporation, FLORSTAB UV12

Organic solvents-

DEGDE … Tokyo Chemicals Co., Ltd, diethylene glycol diethyl ether

-monomers-

PEA … Phenoxyethyl acrylate, Sartomer, SR339C

As shown in tables 2 and 3, the inks of examples 1 to 15, which contain an organic solvent, a polymerizable compound having a weight average molecular weight of 1000 or more and 30000 or less, the specific (meth) acrylic-modified polyorganosiloxane, and the photopolymerization initiator, and in which the content of the organic solvent is 40% by mass or more and 80% by mass or less and the content of the specific (meth) acrylic-modified polyorganosiloxane is 0.1% by mass or more and 5.0% by mass or less, are excellent in IJ ejection stability. The cured images formed in examples 1 to 15 were also excellent in abrasion resistance, and further excellent in flexibility and chemical resistance.

On the other hand, in comparative example 1 in which the content of the specific (meth) acrylic-modified polyorganosiloxane is less than 0.1 mass%, the abrasion resistance of the cured image is lowered.

In comparative example 2 in which the content of the specific (meth) acrylic-modified polyorganosiloxane exceeded 5.0 mass%, the IJ ejection stability of the ink was lowered.

In comparative example 3 in which the content of the organic solvent was less than 40 mass%, the IJ ejection stability of the ink was lowered, and further, the abrasion resistance and the flexibility of the cured image were lowered.

In comparative example 4 in which the content of the organic solvent exceeded 80 mass%, the abrasion resistance of the cured image was decreased, and further, the chemical resistance of the cured image was decreased.

In addition, in comparative examples 5 and 6 in which a polyether-modified polyorganosiloxane or a silicone polyether acrylate was used instead of the specific (meth) acrylic acid-modified polyorganosiloxane, the abrasion resistance of the cured image was reduced.

[ example 101 ]

< preparation of top coating liquid >

Each component having the composition shown in the following table 4 was mixed and stirred by a stirrer manufactured by SILVERSON under conditions of 2,000 rpm to 3,000 rpm and 10 minutes to 15 minutes, thereby preparing a top coat liquid as a colorless ink as a liquid composition for an inkjet printer.

< preparation of ink >

Cyan ink C1 was prepared in the same manner as for the colored ink of example 1, except that polymer 2 was not contained.

A magenta ink M1 was prepared in the same manner as the colored ink of example 13, except that it contained no polymer 2.

A yellow ink Y1 was prepared in the same manner as the colored ink in example 14, except that the polymer 2 was not contained.

A black ink K1 was prepared in the same manner as the colored ink of example 15 except that the polymer 2 was not contained.

< formation of full color cured image >

A full-color cured image (red, blue, green, black test pattern) was formed using cyan ink C1, magenta ink M1, yellow ink Y1, and black ink K1.

Full-color cured images were formed under the same conditions (the same apparatus and the same image forming conditions) as those for the cured image of example 1, except for the type of coloring ink and the image pattern.

< formation of cured image (topcoat film) by topcoat liquid >

The surface coating liquid is filled in an ink jet printer similar to the ink jet printer for forming a full-color cured image, and the surface coating liquid is ejected from an ink jet head of the ink jet printer to print a full-color cured imageSolid images formed with the top coating liquid. At this time, the image density was 1200dpi × 600dpi, and the amount of application of the top coating liquid was 10g/m²。

Then, the base material on which the solid image was printed with the top coating liquid was heated at a base material temperature of 60 ℃ for 10 seconds using a rubber heater, thereby drying the solid image.

Then, the solid image formed by the surface coating liquid after drying was exposed to light at 3000mJ/cm using a UV exposure machine²The solid image formed by the surface coating liquid is cured by irradiating UV (ultraviolet) with the irradiation amount of (b) to obtain a cured image formed by the surface coating liquid (hereinafter, also referred to as "surface coating film").

The top coating film is formed so as to cover the entire full-color cured image.

Hereinafter, the full-color cured image and the top-coat film covering the entire full-color cured image are also referred to as "cured image with a top-coat film".

< evaluation >

The cured image of the above-mentioned surface-coated film or the surface coating liquid was used to perform the following evaluation. The results are shown in Table 4.

(bendability, chemical resistance, IJ discharge stability)

The cured image of the topcoat film was evaluated for flexibility and chemical resistance as described in example 1.

The surface coating liquid was evaluated for the same IJ ejection stability as that shown in example 1.

(abrasion resistance B)

The cured image of the coated film with the surface was evaluated for abrasion resistance (referred to as "abrasion resistance B").

The abrasion resistance B was evaluated in the same manner as in the abrasion resistance a of example 1, except that the evaluation target was changed to a cured image of the coated film with a surface, the load was changed to a load of 400g, and the evaluation criteria were changed as follows. Among the following evaluation criteria, 3 points or more were passed.

Evaluation criteria for abrasion resistance B-

No damage was caused 5 min 20000 times.

The 4 points produced lesions more than 10000 times and less than 20000 times.

The 3-point damage occurred in more than 000 times and less than 10000 times.

2 min produced lesions more than 1000 and less than 5000 times.

1 minute produced lesions in less than 1000 times.

(Adhesivity)

For the cured image of the coated film with a surface, a cross-cut test was carried out in accordance with JIS K5066-5-6: 1992. The cross-cut portion of the cured image of the surface coating film was subjected to an operation of attaching the tape until peeling off (hereinafter referred to as "peeling operation") 3 times. Meanwhile, the portion where the peeling operation was performed was visually observed, and the adhesion of the cured image of the surface coating film was evaluated according to the following evaluation criteria. Among the following evaluation criteria, 3 points or more were passed.

Adhesion-

After 3 times of peeling operation for 5 minutes, no damage was caused on the cured image of the topcoated film.

In 4 minutes, the cured image of the topcoat film was damaged by the 3 rd peeling operation.

In the 2 nd peeling operation, 3 minutes, a scratch was generated in the cured image of the top-coated film.

In the 1 st peeling operation, 2 minutes, a scratch was generated on the cured image of the topcoat film (however, no image peeling was caused).

In the 1 st peeling operation, the cured image of the topcoat film was damaged and peeled off.

Examples 102 to 106 and comparative examples 101 to 104

The same operation as in example 101 was carried out, except that the composition of the top coating liquid was changed to the composition shown in table 4 below. The results are shown in Table 4.

As shown in table 4, the top-coating liquids of examples 101 to 106, which contained an organic solvent, a polymerizable compound having a weight average molecular weight of 1000 or more and 30000 or less, a specific (meth) acrylic-modified polyorganosiloxane, and a photopolymerization initiator, and which contained the organic solvent in an amount of 40 mass% or more and 80 mass% or less and contained the specific (meth) acrylic-modified polyorganosiloxane in an amount of 0.1 mass% or more and 5.0 mass% or less, exhibited excellent IJ ejection stability. The cured images of the band-side coating films formed in examples 101 to 106 were excellent in abrasion resistance, and further excellent in flexibility, chemical resistance, and adhesion.

On the other hand, in comparative example 101 in which the content of the specific (meth) acrylic acid-modified polyorganosiloxane was less than 0.1% by mass, the abrasion resistance of the cured image of the surface-coated film was lowered.

In comparative example 102 in which the content of the specific (meth) acrylic acid-modified polyorganosiloxane exceeded 5.0 mass%, the IJ ejection stability of the top-coating liquid was lowered.

In addition, in comparative examples 103 and 104 in which a polyether-modified polyorganosiloxane or a silicone polyether acrylate was used instead of the specific (meth) acrylic-modified polyorganosiloxane, the abrasion resistance of the cured image of the surface coating film was reduced.

The entire disclosure of japanese patent application No. 2015-248005, filed 12/18/2015, is incorporated by reference into this specification.

All documents, patent applications, and technical standards described in the present specification are incorporated by reference into the present specification to the same extent as if each document, patent application, and technical standard was specifically and individually described to be incorporated by reference.

Claims

1. A liquid composition for an ink jet printer, which contains an organic solvent, a polymerizable compound having a weight average molecular weight of 1000 to 30000 inclusive, a (meth) acrylic acid-modified polyorganosiloxane which is a copolymer of a reactive polysiloxane having at least one of a polymerizable group and a mercapto group and which does not have a polymerizable group and has a weight average molecular weight of 20000 to 400000 inclusive, and a photopolymerization initiator,

the content of the (meth) acrylic acid-modified polyorganosiloxane is 0.1 to 5.0% by mass based on the total amount of the liquid composition,

the polymerizable compound is a compound having a polymerizable group, and the polymerizable group is a group containing an ethylenic double bond or an epoxy group.

2. The liquid composition for an inkjet printer according to claim 1, wherein the polymerizable compound is a 2-functional acrylate compound.

3. The liquid composition for an inkjet printer according to claim 1, wherein the content of the polymerizable compound is 5% by mass or more and 40% by mass or less with respect to the total amount of the liquid composition.

4. The liquid composition for an inkjet printer according to claim 1, comprising particles composed of the (meth) acrylic acid-modified polyorganosiloxane, wherein the volume average primary particle diameter of the particles is 0.01 μm or more and 0.3 μm or less.

5. The liquid composition for an inkjet printer according to claim 4, wherein the polymerizable compound is a 2-functional acrylate compound, and the content thereof is 5% by mass or more and 40% by mass or less with respect to the total amount of the liquid composition.

6. The liquid composition for an ink jet printer according to claim 1, wherein the reactive polysiloxane is at least one of compounds represented by the following formula (I),

[ chemical formula 1]

In the formula (I), R¹、R²And R³Independently represents a C1-20 alkyl group, a C1-20 halogenated alkyl group, or a C1-20 alkoxy group, Y represents an organic group having at least one of a polymerizable group and a mercapto group, Z¹And Z²Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by the formula (Z), m represents an integer of 1 to 10000, n represents an integer of 1 or more,

7. The liquid composition for an inkjet printer according to claim 6, wherein the liquid composition comprises particles of the (meth) acrylic acid-modified polyorganosiloxane, the particles have a volume average primary particle diameter of 0.01 to 0.3 μm, and the polymerizable compound is a 2-functional acrylate compound, and the content thereof is 5 to 40 mass% based on the total amount of the liquid composition.

8. The liquid composition for an ink jet printer according to claim 6, wherein Y in the formula (I) is a mercaptoalkyl group having 1 to 20 carbon atoms,

the R in the formula (Z)⁶Is a C1-20 hydrocarbon group, a C1-20 halogenated hydrocarbon group, a C1-20 hydrocarbyloxy group, or a C1-20 mercaptoalkyl group.

9. The liquid composition for an ink jet printer according to claim 7, wherein Y in the formula (I) is a mercaptoalkyl group having 1 to 20 carbon atoms,

10. The liquid composition for an inkjet printer according to any one of claims 1 to 9, wherein the (meth) acrylate is at least one compound represented by the following formula (II),

[ chemical formula 2]

In the formula (II), R⁷Represents a hydrogen atom or a methyl group, R⁸Represents an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.